Bis-triazinylaminostilbene compounds



Patented Sept. 13, 1966 amino groups, i.e. that yellowed organic material, in par- 3,272,805 ticu-lar cellulose material, can be given a more pleasant,

BISIRIAZINYLAMINOSTILBENE COMPOUNDS H an" dJ k bB' d] R h S ta: Whiter appearance einrlc ausermaun an a In 81 1e en Wl er- 0t d b d t 1 h t but, for exam 16, land, assignors to It. R. Geigy A.G., Basel, Swit zerland an n use y m us na 0 emls S P No Drawing. Filed y 2 1964 Ser. No. 380,033 5 by a housewife, many of the previously known optical brightening agents having a basis of 4,4'-bis-triazinyl- Chums Enemy i ggfig g July 1960 aminostilbene compounds have great disadvantages. 6 (CL 2 0-240 Often the drawing power is insufficient at the relatively low application temperatures preferred in such non-indus- This application is a continuation-in-part of our co- 10 trial uses. If, on the other hand, products having particpending application Serial No. 127,098, filed on July 27, ular atfinity to the fibers are used under the conditions 1961, now abandoned. described, spots due to bad levelling power occur on the The present invention concerns new 4,4'-bis-triazinylat1'ea ted q Also, the Willa-Solubility 9 Products minostilbene compounds, processes for the production havlng afllfllty f the fibers Ofifin too sllght at low thereof, their use for the optical brightening of organic 15 temperatures whlch also calls Spots to appear on the material, in particular of cellulose material, agents havtreated matenalsing a content of such compounds, as well as, as industrial It 110W P6611 u d that these disadvantages can product, the material brightened therewith be ellmlnated 1n householduse 1f 4,4 :blS-tI'haZHIYlEimIHO- It is Well known that white ,[eXtfle mawrial such as strlbene compounds according to the invention are used.

mens shirts, ladies white dresses, underwear, bedlinen ,9929% gg fs g g gi fi i i 1 8 8? and the like are given a Whiter appearance by adding to ainino)-stilberie-2 2'-disulf onic acid or the salts thereof 2? gigg i gfizr gi is ig $12 3 833;; possibly in the presence of buffer salts, in steps and in any order esired with 2 mols of a rimar aromatic amine of textile cellulosic materials, in particular cotton m-atenals, the general formula p y are given increasing contents of textile finishes 1n the form of synthetic resins, for instance as anti-crease finish 2 n in dry state, and so-called non-resin finishes which yield to form a compound of the general formula A--NH NHA SOaH l CN I NC Ni ONH-C OH=OHNHO N (IIZN s o H YO(CH2)DNH a NH(GHa)u-OY (II so-called cross-linked cellulose as anti-crease finish in wet In Formulae I and II aff i i g fi to i 1y fi i 5 21233 5; A represents a radical of the benzene series, ifiinilttafi as: as: at Y an at most 2 least the same r referably even whiter whitening atoms or an alkoxyalkyl radical in which the alkoxy effect P group and the alkyl group each have at most 2 carbon D t However, in applying such lncreased amounts of n 2 32 33 3 5; whole number of 2 to 3 brightening agents, particularly those of the bistriazinylstilbene series, to the modern textile materials, the latter adopt an undesirable g h shade, whi h becomes ever it can also contain substituents, for example the more and more pronounced, the more often the material methyl grou the methoxy group; halogens such as, has been washed. Such undesirable effect appears in hl i particular with the modern synthetic so-called non-soap A particularly valuable class of 4,4'-bis-triazinylaminodetergents as they are used, in particular in powder form stilbene compounds according to the invention are those in the operation of automatic washing machines, and of the formula A is preferably an unsubstituted phenyl radical. How- A-NH NH-A SOsH CN NC N CNHCH=CH-NHO N C=N NO l sous: Y-O(CH2) DNH NH(CH) u 0 Y also, especially, in the preferred washing of laundry at low wherein range temperatures of about 25 to 40 C.

Moreover, the above-mentioned optical brighteners, A 22 5223 ZF 25???fiigi iggzfi i ifg f Ziggy? especially those of the above-mentioned series which bear phenyl 1 0 r uphenyl g g y their mo1.ecu1es.hydroxyalkylimino Substituents at the Y represents a member selected from the gro ilp consisting triazlnyl radlcals, impart to the non-soap detergents an of methyl ethyl methoxyethyl ethoxyethyl and undeslrable yellowish to greenlsh aspect, while the public in this country demands the purest, Whitest possible 5 n Is one of the Integers 2 and aspect of such non-soap detergents for use in washing machines The following are examples of aromatic amines used It is also known that the appearance of textile cellulose according to the invention:

materials can be improved by treating them with 4,4-bistriazinylaminostilbene-2,2-disulfonic acids or the wateramino-benzene, 2-, 3- or 4-methyl-1-aminobenzene, 2,4- or soluble salts thereof each triazine ring of which contains 2,5-di=methyl-l-aminobenzene, 2- or 3-methoxy-1-amir1oat least one and preferably two organically substituted benzene, 2-, 3- or 4-chloro-1-aminobenzene.

Examples of compounds of Formula I are:

2-methoxyethylamine, 2-ethoxyethylamine,

3-methoxypropylamine, 3-ethoxypropylamine,

2-(B-methoxyethoxy-ethylamine,

2- fl-ethoxyethoxy) -ethylamine, 3- fi-methoxyeth oxy) propylarnine or 3-(fl-ethoxyethoxy)-propylamine.

In the first step, the 4,4-bis-(4",6"-dihalogen-1",3, 5"-triazinyl- (2" -amino) -sti1bene-2,2'-disulphonic acid is reacted preferably in the form of its water soluble salts in aqueous solution at 5-60 C. and, in the second step it is reacted at 70-100" C. by known methoxy with the amino compounds used according to the invention, possibly in the presence of alkali metal salts of low fatty acids or of carbonic acid such as, e.g., sodium acetate or sodium carbonate, as agents buffering the mineral acid.

The amines of Formula I used according to the invention are obtained, for example, by reacting esters, obtained from corresponding hydroxy compounds with strong acids such as halogen hydracid, with ammonia under pressure.

The new triazinylstilbene compounds according to the invention ares isolated from the reaction mixture preferably in the form of their alkali metal salts which, after drying, have good water solubility. In aqueous and in neutral or alkaline washing liquors they have good afiinity to cellulose material and good levelling power. Compared with the previously known 4,4-bis-(diaminotriazynamino]-stilbene-2,2'-disulphonic acid formed and the acid liberated is neutralised by the simultaneous addition of an aqueous solution of 27 parts of sodium carbonate. The yellowish suspension is then stirred at room temperature (-25) until the aminobenzene has completely disappeared. 56 parts of 3-methoxypropylamine are then added and the alkaline mixture is stirred at 8590 until a sample thereof no longer turns phenolphthaline paper red. The temperature is then raised to 90 and a solution of 20 parts of sodium hydroxide in 30 parts of water is added to the reaction mixture within 1 hour. After stirring for another hour at 90-95 175 parts of sodium chloride are added. The reaction product of the formula given above which is formed separates in liquid form as a heavy, yellowish mass and is decanted from the aqueous phase. On cooling, the product solidifies into a solid, yellowish mass which decomposes into a powder on drying. In aqueous solution in daylight, the new brightening agent has a blue to blue-violet fluorescence depending on the degree of dilution and, in spite of its very good water solubility, it has excellent affinity to cellulose fibres. If the product is incorporated into a usual marketed washing agent, then cellulose materials washed therewith are very beautifully optically brightened even when the washing is performed under mild conditions If in this example, the 46.5 parts of aminobenzene are replaced by 53.5 parts of 3-methyl-l-aminobenzene or 61.5 parts of 3-methoxy-l-aminobenzene, then brightening agents with similar properties are obtained.

EXAMPLE 2 /C N\ /N(i1\ C=N N=C I S O 3N3 S 0 3N3 (321150 CHzCHr-NH NH-CHzCHzO C1115 85.2 parts of the sodium salt of 4,4-bis-[4"-chloro-6"- 40 (p methylphenylamino) 1",3",5" triazinyl (2")- amino]-stilbene-2,2'-disulphonic acid (produced under the conditions given in Example 1) are distributed in 2500 parts of water while stirring and, after the addition of 22 parts of 2-ethoxyet-hylamine, are stirred for 20 minutes at 90. The temperature is then raised to -95 and a solution of 8 parts of sodium hydroxide in 20 parts of water is poured in within 2 hours. The reaction mixture is stirred another hour at 90-l00 and then parts of sodium chloride are added. After cooling, the reaction 93 parts of cyanuric chloride are dissolved in 450 by volume of acetone. The solution is poured, while stirring, into 2250 parts of ice/Water. A solution of 103.5 parts of the sodium salt of 4,4-diaminostilbene- 2,2'-disulphonic acid and 27 parts of sodium carbonate in 1200 parts of water is poured, within 1 hour while stirring well at 0-5 into the cyanuric chloride suspension so obtained. A solution of 46.5 parts of aminobenzone in 50 parts by volume of acetone is added dropwise at 5-15 to the yellowish suspension of the dis-odium salt of 4,4 bis-[4",6" dich'loro 1",3",5" triazinyl (2.")- 75 parts 65 product which separates is filtered off. It is washed with a 5% sodium chloride solution and the product is dried at 89-90" under vacuum. In this way the disodium salt of 4,4 bis [4" (B ethoxyethylamino) 6" (pmethylphenylamino) 1,3,5 triazinyl (2") ami- 7 no]-stilbene-2,2-disulphonic acid is obtained as a yellow powder which dissolves well in water. In daylight, the a diluted aqueous solution of this product fluoresces blue to blue-violet. The product is excellently suitable as additive to washing agents.

Products very well suited for the purpose mentioned are also obtained if, in this example, the 22 parts of 2- ethoxyethylamine are replaced by 18.5 parts of 2-methoxyethylamine, 22 parts of 3-rnethoxypropylamine or by 33 parts of B-(fi-methoxyethoxy)-propylamine. The latter amine is obtained by adding acrylonitrile to ethylene glycol monomethyl ether and then catalytically hydrogenating. B.P. 7678.

are replaced by 33 parts of 2-(B-ethoxyethoxy)-ethylamine, then brightening agents which are also valuable for the purpose mentioned are obtained.

The Z-(B-ethoxyethoxy)-ethylamine is obtained from 2-(fi-ethoxyethoxy)-ethyl chloride (produced from diethylene glycol monoethyl ether and SOCl by heating in an autoclave with ammonia at 120.

EXAMPLE 5 l OH E -Q C-N N-C C==N N=C l S O 3N3. S 0 3N3 I CHaOCHzCHaNH NHCHzCHzO CH EXAMPLE 3 fi t Q /CN\ /N- O\\ C=N N=G S 0 3N3 S OaNa CHaOCHzCHzNH NHOHzOHzOOHa 177 parts of the sodium salt of 4,4'-bis[4",6"-dichloro- 1,3",5" triaZinyl-(2)-amin0] -stilbene-2,2'-disulphonic acid are distributed while stirring in 3000 parts of water and 38.5 parts of Z-methoxyethylamine are added within 30 minutes at After raising the temperature to 40, an aqueous solution of 26.6 parts of sodium carbonate is poured in over a period of 1 to 2 hours in such a manner that the pH of the reaction mixture is always 7 to 8. 46.5 parts of aminobe-nzene are then added to the practically clear solution of the disodium salt of 4,4'-bis-[4"-chloro-6-(fl-methoxyethylamino)-1", 3",5" triazinyl (2") amino]-stilbene-2,2-disulphonic acid formed and the whole is refluxed for 5 hours while 40 stirring. After the pH of the reaction mixture has been adjusted to 10-11 by the addition of sodium hydroxde, the product of the formula given above is separated out by the addition of 150 parts of sodium chloride, isolated and dried in vacuo at 70-90. A yellowish powder which easily dissolves in water is obtained. It has properties similar to those of the compounds produced according to Example 1.

Very valuable products are also obtained if, in this example, the 465 parts of aminobenzene are replaced by 53.5 parts of 3-methyl-1-aminobenzene or by 61.5 parts of 3-methoxy-l-aminobenzene.

EXAMPLE 4 SOaNa SOaNa I CzHsO C H2 0 HRNH 82.3 parts of the sodium salt of 4,4-bis[4"-chloro-6- phenylamino 1",3",5"-triazinyl (2")-amino]-stilbene- 2,2-disulphonic acid (produced under the conditions sodium chloride and has the formula given above. After drying, it is a pale yellowish powder which dissolves well in water and has properties similar to those of. the compounds produced according to Examples 1 to 3. The product is also suitable as additive to washing agents.

71 parts of the sodium salt of 4,4-bis-[4",6"-dichloro- 1,3,5 triazinyl-(2")-amino]-stilbene-2,2'-disulphonic acid are distributed, while stirring, in 1500 parts of water and 25.5 parts of 3-chloro-1-aminobenzene are added at 2030. The pH of the mixture is kept at 6.5-7 by the gradual addition of aqueou sodium hydroxide solution and the whole is stirred until no more 3-chloro-1-aminobenzene can be traced for practical purposes by diazotising and coupling a sample.

18.5 parts of Z-methoxyethylamine are then added to the yellowish suspension of the disodium salt of 4,4'-bis- [4" chloro 6"-(m-chlorophenylamino)-1",3",5"-triazinyl (2") amino]-stilbene-2,2'-disulphonic acid obtained. The whole is stirred and heated to 90 and an aqueous solution of 8 parts of sodium hydroxide are added within 2 hours. After adding 75 parts of sodium chloride, the solution is cooled whereupon the reaction product, which was at first liquid, solidifies. It is filtered off under suction and dried in vacuo at 60-80. The disodium salt of 4,4-bis-[4"-(,B-methoxyethylamino)-6"- (m chlorophenylamino) 1",3",5 triazinyl (2")- amino]-2,2-disulphonic acid so obtained is a yellowish powder which dissolves easily in water; it is excellently suited for the optical brightening of white cotton fabrics in washing liquors.

Equally-active products are obtained if in this example, the Z-methoxyethylamine is replaced by 22 parts of 3- methoxypropylamine or if the 3-chloro-l-aminobenzene is replaced by the same amount of 4-chloro-1-aminobenzene. In the latter case, a somewhat more diflicultly soluble product is obtained.

Other optical brightening agents which are suitable for combination with washing agents for the brightening of cellulose fibres are obtained if 1 mol of the sodium salt of 4,4'-bis-[4",6"-dichl0ro-1",3",5"-triazinyl-(2")- amino]-stilbene-2,2'-disulphonic acid is successively re- If, in this example, the 22 parts of 2-ethoxyethylamine 75 acted in the manner described above with 2 mols of each of the following arylamines and alkoxyalkylamines:

Table I No. Arylamine Alkoxyalkylamine 1 Amlnobenzene CH OCH CHzOCHzCHzNHz 2 do- CHaOCHzCEUOCHzCHzCHzNH; 3 d CzHOCHzCH2CH2NHn 4 3-methyl-1-aminobenzene CHaOCHzCHzOCHzCHzCHzNHz 5 d0 C2H5OCHCH2NH2 6 4-methyl4-aminobenzene. C2H5OCH2CH2CH2NHQ 7 3-methoxy-1-aminobenzene CzHsOCHzClLNHz 8 0 C2II5OOH2CHzOCHzCHzNH 9 4-chloro-1-aminobenzene CH3OCHZCH2CHQNH2 10 0 CHaOCHzCHzOCHzOEhNHz *This amine is produced from B-methoxyethoxyethyl ch10- rlde (produced from diethylene glycol monomethyl ether and SOCla) by heating in an autoclave with ammonia at 120.

EXAMPLE 6 A heavy-duty non-soap detergent mixture consisting of 8 parts of lauryl sulfate, 11 parts of dodecylbenzene sulfonate, 11 parts of sodium tripolyphosphate, 17 parts of tetrasodium pyrophosphate and 37 parts of sodium sulfate is worked up into a paste with a solution of 0.1 part of the sodium salt of 4,4'-bis-[4"-(/3-ethoxyethylamino) 6" (p methylphenylamino) 1",3",5-triazinyl-(2")-amino] -stilbene-2,2'-disulfonic acid described in Example 2 in 170 parts of water. This paste is then dried at 60 and then milled. In daylight, the washing powder obtained has a considerably whiter appearance than the same washing composition produced without the addition of the optical brightening agent.

Beautiful white washing powders are also obtained if, instead of the brightening agent mentioned above, the same amount of the sodium salt of 4,4'-bis-[4"-('ymethoxypropylamino) 6" phenylamino 1",3",5"- triazinyl-(2)-amino]-stilbene-2,2' disulfonic acid obtained according to Example 1 or of the 2-methoxyethylamine derivative produced according to Example 3 are incorporated into the above washing agent preparation.

EXAMPLE 7 1 part of household linen is washed for 20 minutes at 60 with 10 parts of a washing liquor which contains 8 g. per liter of the washing agent produced according to Example 6. The goods are then rinsed and dried. In spite of the relatively low washing temperature, a dazzling white wash is obtained.

EXAMPLE 8 A heavy duty detergent mixture consisting of 7.8 parts by weight of lauryl sulfate,

110 parts by weight of dodecyl benzene sulfonate,

11.0 parts by weight of sodium tripolyphosphate 16.6 parts by weight of tetrasodium pyrophosphate,

4.6 parts by weight of anhydrous sodium silicate,

1.4 parts by weight of carboxymethyl cellulose,

36.8 parts by weight of sodium sulfate,

8.0 parts by weight of sodium perborate (NaBO -4H O),

and

0.3 part by weight of disodium 4,4'-bis-[4"-(fi-methoxyethylarnino)-6"-phenylamin0-1",3",5"-triazinyl-(2")- amino]-stilbene-2,2'-disulfonate produced as described in Example 3, supra, is produced in the following manner.

The optical brightener is intimately mixed with normal aqueous sodium hydroxide solution (10 ml. per g. of brightener) and when the brightener is thoroughly dispersed, about 200 to 300 ml. of water (per gram of brightener) are added.

The other ingredients of the detergent mixture are mixed with each other separately and intimately using a sufficient amount of water to obtain a creamy paste, the latter is dried at 60 and granulated.

The detergent granules are then added to the slurry of brightener and the mixture is repeatedly and thoroughly stirred until a smooth, creamy mix is obtained. The resulting slurry is then spread into a uniform layer on a flat surface and dried in an oven at for 16 hours. The resulting cake is allowed to cool to room temperature, left standing for at least 30 minutes and then crushed and placed in a desiccator. The dried chunks of detergent mixture are then forced through a 20 mesh screen and, if desired, the resulting powder is transferred to 60 mesh screen to remove the fine portion.

EXAMPIJE 9 In a similar manner as described in Example 8 there is produced a synthetic, non-soap, heavy-duty detergent of Disodium 4,4-bis[-4-(B-ethoxy ethylamino)-6" phenylamino 1",3",5",-triazinyl-(2") amino]- stilbene-2,2'-disulfon ate EXAMPLE 10 A heat-liquifia-ble soap for use in washing machines is produced as follows:

To a hot mixture of 40 parts by weight of coconut oil fatty acid sodium soap 31 parts by weight of sodium tripolyphosphate 9 parts by Weight of tetrasodium pyrophospate 6 parts by weight of sodium silicate 3 parts by weight of magnesium silicate 0.5 part by weight of sodium ethylenediamine tetraacetate 5 parts by weight of sodium carbonate 5.5 parts by weight of sodium sulfate and 70 parts of water there is added 0.4 part by weigh-t of disodium 4,4'-bis- [4"-(fi-methoxyethylamino) 6" (m methylphenylamino)-1,,3,5"-triazinyl-(2")-amino] stilbene 2,2- disulfonate, mixed intimately and then dried in a spray tower.

A beautiful white, free-flowing washing powder is obtained which brightens anti-crease finished cotton increasingly with successive washings, and without greenish shade in spite of accumulation of the brightening agent on the fiber.

EXAMPLE 11 A non-ionogenic washing agent was prepared by intimately mixing with each other the following ingredients Parts by weight terials imparting to the same a pure white appearance Nonylphenol polyglyc-olether with 15 ethylenoxy which does not develop a greenish hue even after 20 groups l1 washings.

Water 11 Sodium tripolyphosphate 33 EXAMPLE 13 T tra odi pyrophgsphate 11 A lrghtduty non-soap detergent of similar good props di ili erties is obtained by repeating the preceding Example 12, s di lfat 20 but using instead of the brightening agent contained there- Sodium carbonate 2 in 0.4 part by weight of disodium 4,4'-bis-[4"-(/3-ethoxy- Carboxymethyl cellulose 2 10 ethy1amino)-6"-(m methoxyphenylamino) 1",3",5"

triazinyl- (2" -am'in0] -stilbene-2,2-disulfonate.

s-tilbene-Q,2-disulf0nate 0.5 EXAMPLE 14 This washing agent is a powder of similar good prop- A heavy t nomsoap good. White. erties as the agents described in the preceding example. 15 peara'nce Improved solubl'hty P Water 15 obt'imed Especially it is distinguished by a brilliant white appearby repeaunjg Exampljc 9 but usmg f of g ance ener contamed thereln, 0.5 part by welgh t of disodium salt of 4,4-bis- [4"{5- [2-met-hoXy-ethoxy] -ethylamin-o) EXAMPLE 12 6-phenylamino-1",3",5"-triazinyl (2") amino]-stilbene-2.2-disulfonate. In order to produce a light duty, non-soap detergent, We claim: the following ingredients are mixed together 1. A compound of the formula A-NH | S0311 i NO N o-NH-oH=0H--NH 0 N o=N 1 N=C I H035 i Y-O-(CHnh-NH Y-O-(CH2)n-NH Parts by weight Sodium dodecyl-benzene sulfonate 20 h Sodium laurylsulfate 8 W erem Laurie acid mono-N-B-hydroxyethylam-ide 2 A represents a member Selected from the group 6011' sodium .tripoIy-phosphate 3 sisting of p y -m t y ph nyl, 4-methy1 henyl CarboXy-methyl cellulose 1.5 yp y Sodium sulfate 60.5 Y represents a member selected from the group consist- 4,4'-bis-[4"-(B-methoXy-ethylamino) 6"-(p-meth- 40 g of methyl and y aJld yl henylarnino)-1",3",5" triazinyl-(2")-arnin0] n is one of the integers 2 and 3. stilbene-2,2-disulfonic acid 0.35 2. The 4,4-bis-triazinylaminostilbene compound of the Water 80 formula Q Q 30311 I N CNH--CH=CHC NHO N l N=C I SOsH CH3O-CH2OH2NH NHCH2CHz-OCH;

whereby a homogenous slurry is obtained which is dried 3. The 4,4'-bis-triazinylaminostilbene compound of the at C. and pulverized. formula Q 30311 5 O-N\ N0 CH 3 N ONH 011:011- NHC N 3 C=N \N=C SOaH CH3-OCH2CH5NH NH-CHz-CHz-OCHa The resulting powder has a brilliant white appearance 4. The 4,4'-bis-triazinylaminostilbene compound of the and can be used for washing white cotton or rayon maformula GHQ-Omen NH-OCH; S0311 I I N CNH-CH=CHNHO N C=N N=O SOaH I CHaCHzO-CHzCHa-NH NH-CHzCHt-O CH2CH3 5. The 4,4'-bis-triazinylaminostilbene compound of the formula 6. The 4,4'-bis-triazinylaminostilbene compound of the formula SlOQH SOzH I NH-CHz-CHz-CHg-OCH;

References Cited by the Examiner UNITED STATES PATENTS 2,667,458 1/1954 Adams et a1 260-2496 X 3,047,390 7/1962 Koerber et a1. 260249.6 X 3,051,704 8/1962 Gehm 260-2496 X 3,177,207 4/1965 Siegel et a1 260-240 OTHER REFERENCES 1,015,806, September 1957, Germany (German Auslegeschrift, 4 pages).

JOHN D. RANDOLPH, Primary Examiner. 

1. A COMPOUND OF THE FORMULA 